Imitation pilose leather sheet and manufacturing method thereof

Abstract

The imitation pilose leather sheet involved in the embodiment includes: a fibrous substrate composed of a textile or a knitted fabric; and a mixture applied to the fibrous substrate and containing a silicone resin and a polyurethane resin. The imitation pilose leather sheet is configured such that a pilose surface having pilose hairs is provided on the surface of the sheet, and the pilose hairs are composed of the fibers constituting the textile or the knitted fabric and the above mixture is attached thereto. The length of the pilose hairs is 200 to 500 μm, and the static friction coefficient when the pilose surfaces are rubbed against each other is 0.660 to 1.300.

Description

Technical Field

[0001] The present invention relates to a flocked leather-like sheet and a method for manufacturing the same. Background Art

[0002] Conventionally, leather-like sheets used for vehicle interior materials such as seat covers and door linings, home improvement materials such as furniture and chairs, and fashion items such as bags and shoes are manufactured by applying synthetic resins (polyurethane resin, vinyl chloride resin) to fibrous substrates such as non-woven fabrics, knitted fabrics, and woven fabrics. Leather-like sheets have the following problem: when the surface smoothness is insufficient, a frictional sound is generated during surface friction.

[0003] Patent Document 1 discloses a synthetic leather that, for the purpose of preventing the generation of frictional sound, has a surface treatment layer formed of a polyurethane containing an organosilicon oil and / or a modified organosilicon oil and including organosilicon diol in the polyol component on the surface of the polyurethane skin layer.

[0004] On the other hand, for leather-like sheets, it is known to use a combination of polyurethane resin and organosilicon resin. For example, Patent Document 2 discloses a synthetic leather obtained by sequentially laminating a polyurethane adhesive layer, a lower polyurethane skin layer, an upper polyamino acid resin skin layer, and a surface treatment layer of a crosslinked silicone resin on the surface of a substrate.

[0005] In addition, for flocked leather-like sheets such as suede leather-like sheets, it is also known to apply a polyurethane resin and an organosilicon resin to a substrate made of a non-woven fabric. Patent Document 3 describes the following: for an ultrafine flocked sheet made of a non-woven fabric with at least one side flocked, a complex formed of a low molecular weight polyurethane and an organosilicon resin is applied to its surface. Patent Document 4 describes artificial leather obtained by attaching a solution containing a polyurethane resin raw material, polyvinyl alcohol, and an organosilicon resin to a non-woven fabric reinforced with a knitted fabric or a woven fabric. Patent Document 5 describes a sheet containing a self-emulsifying polyurethane and a film-forming organosilicon in a non-woven fabric composed of ultrafine fibers.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 02-277891

[0009] Patent Document 2: Japanese Patent Laid-Open No. 62-215080

[0010] Patent Document 3: Japanese Patent Laid-Open No. 2004-315986

[0011] Patent Document 4: Japanese Patent Laid-Open No. 2004-332173

[0012] Patent Document 5: Japanese Patent Application Laid-Open No. 2012-046863 Summary of the Invention

[0013] As described above, for artificial leather sheets, it is known to use a combination of a polyurethane resin and a silicone resin. However, it is unknown that the use of a combination of a polyurethane resin and a silicone resin suppresses frictional noise.

[0014] Generally, frictional noise poses a problem for artificial grained leather sheets, but has not been a problem for artificial raised leather sheets so far. However, the inventors of the present invention believe that in view of the recent development of vehicle noise reduction, artificial raised leather sheets will be required to suppress frictional noise at a high level in the future.

[0015] In addition, the above-described conventional artificial raised leather sheets using non-woven fabrics are likely to shed hairs due to abrasion, and the hair shedding resistance and abrasion resistance are poor.

[0016] The present invention has been made in view of the above circumstances, and an object thereof is to improve the hair shedding resistance and abrasion resistance and suppress the generation of frictional noise for artificial raised leather sheets.

[0017] The artificial raised leather sheet according to an embodiment of the present invention includes: a fibrous substrate composed of a woven fabric or a knitted fabric; and a mixture applied to the fibrous substrate and containing a silicone resin and a polyurethane resin. The artificial raised leather sheet is configured to have a raised surface with raised hairs on the surface of the sheet, and the raised hairs are composed of fibers constituting the woven fabric or the knitted fabric and are attached with the mixture. The length of the raised hairs is 200 to 500 μm. The static friction coefficient when the raised surfaces are rubbed against each other is 0.660 to 1.300. The mixture exists at least on the surface side where the raised hairs are present in the thickness direction of the fibrous substrate. The length of the raised hairs is the length of the raised hairs in a state where the mixture is attached. The silicone resin has a three-dimensional network structure of a siloxane skeleton.

[0018] A method for manufacturing a faux-pilo leather sheet according to an embodiment includes: (1) forming pilo on at least one surface of a fibrous substrate composed of a textile or a knitted fabric, the pilo being composed of the fibers constituting the textile or the knitted fabric, and (2) applying a mixture containing a silicone resin and a polyurethane resin to the fibrous substrate on which the pilo is formed, thereby obtaining a faux-pilo leather sheet. The surface of the faux-pilo leather sheet has a pilo surface having pilo to which the mixture is attached. The length of the pilo is 200 to 500 μm, and the static friction coefficient when the pilo surfaces are rubbed against each other is 0.660 to 1.300. In the faux-pilo leather sheet, the mixture is present at least on the surface side where the pilo exists in the thickness direction of the fibrous substrate. The length of the pilo is the length of the pilo in a state where the mixture is attached. The silicone resin has a siloxane skeleton with a three-dimensional network structure.

[0019] In the above embodiment, it is sufficient that the silicone resin has a siloxane skeleton with a three-dimensional network structure at the stage of forming the faux-pilo leather sheet, and it may not have a three-dimensional network structure at the stage before formation. In addition, applying the mixture to the fibrous substrate means: making it a state where the mixture is applied to the fibrous substrate by methods such as dipping, coating, spraying, or printing.

[0020] Advantages of the Invention

[0021] According to the present invention, it is possible to provide a faux-pilo leather sheet that suppresses the generation of friction noise and improves the fluff resistance and wear resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a schematic cross-sectional view of a faux-pilo leather sheet according to an embodiment. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0023] The faux-pilo leather sheet according to the present embodiment is a sheet including a fibrous substrate formed of a textile or a knitted fabric, and a mixture containing a silicone resin and a polyurethane resin (hereinafter sometimes simply referred to as "resin mixture") applied to the fibrous substrate. The sheet has a pilo surface having pilo on the surface of the sheet. The pilo is composed of the fibers constituting the above-mentioned textile or knitted fabric and is attached with the resin mixture.

[0024] Figure 1 is a cross-sectional view schematically showing an example thereof. Figure 1The shown pilose imitation leather sheet 10 includes a fibrous substrate 12, which is composed of a textile or a knitted fabric. A mixture of a silicone resin and a polyurethane resin (not shown) is applied to the entire fibrous substrate 12. On the surface of the sheet 10, there are erected hairs 14 composed of the fibers of the textile or knitted fabric constituting the fibrous substrate 12. On the surface of the fibers of the erected hairs 14, the resin mixture is adhered. On the surface of the sheet 10, a pilose surface 16 is formed, and the pilose surface 16 has the erected hairs 14 to which the resin mixture is adhered.

[0025] In the present embodiment, since the fibrous substrate is composed of a textile or a knitted fabric, it is possible to suppress lint shedding and improve wear resistance. The fibrous substrate is more preferably a knitted fabric. It should be noted that the fibrous substrate may be colored with a dye or a pigment.

[0026] As the fibrous substrate, a fibrous substrate having erected hairs on the surface, that is, a fibrous substrate having a pilose surface is used. That is, erected hairs are formed on at least one surface of the fibrous substrate. The erected hairs are composed of the fibers of the textile or knitted fabric and are bound to the textile structure or the knitted structure, so that the effect of improving lint resistance and wear resistance can be improved. The erected hairs refer to the hairs (fluffs) provided on the surface of the fibrous substrate and are also called hairy.

[0027] The fineness (single fiber fineness) of the fibers constituting the erected hairs is not particularly limited, and is preferably 0.1 to 0.4 dtex. By the single fiber fineness being 0.1 dtex or more, the wear resistance is good. By the single fiber fineness being 0.4 dtex or less, the touch is good and the effect of preventing abnormal noise is obtained.

[0028] The fiber raw material constituting the fibrous substrate is not particularly limited, and conventionally known natural fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers, etc. can be used. These fiber raw materials can be used alone or in combination of two or more. Among them, from the viewpoints of durability, particularly mechanical strength, heat resistance, and light resistance, the fiber raw material is preferably a synthetic fiber, more preferably a polyester fiber, and particularly preferably a polyethylene terephthalate fiber.

[0029] The fineness (yarn fineness) of the yarn constituting the fibrous substrate is not particularly limited, and is preferably 50 to 200 dtex. By the yarn fineness being 50 dtex or more, the wear resistance is good. By the yarn fineness being 200 dtex or less, the touch is good and the effect of preventing abnormal noise is obtained.

[0030] The thickness of the fibrous substrate is not particularly limited and can be, for example, 600 to 1500 μm. More specifically, when the fibrous substrate is a textile fabric, the thickness of the fibrous substrate is preferably 600 to 1500 μm, more preferably 800 to 1200 μm. When the fibrous substrate is a knitted fabric, the thickness of the fibrous substrate is preferably 600 to 1300 μm, more preferably 800 to 1200 μm. By setting the thickness of the fibrous substrate to be not less than the lower limit value, good abrasion resistance can be obtained. By setting the thickness of the fibrous substrate to be not more than the upper limit value, good hand feeling can be obtained. It should be noted that the above thickness of the fibrous substrate is the thickness of the fibrous substrate before applying the silicone resin and the polyurethane resin. However, the thickness of the fibrous substrate in the simulated shag leather sheet after applying the resin can be set within the same range.

[0031] The thickness of the fibrous substrate is the value measured by a constant-pressure thickness gauge (e.g., Ozaki Seisakusho Co., Ltd.: Peacock Micrometer H-30) according to the JIS L1096 8.4A method (JIS method), and it is the thickness measured in a manner that also includes the raised hair part.

[0032] The density of the fibrous substrate is not particularly limited. When the fibrous substrate is a textile fabric, the density of the fibrous substrate is preferably: warp density 150 to 400 threads / 25.4 mm, weft density 50 to 150 threads / 25.4 mm. When the fibrous substrate is a knitted fabric, the density of the fibrous substrate is preferably: 30 to 90 rows / 25.4 mm, 20 to 60 holes / 25.4 mm. By setting the density of the fibrous substrate to be not less than the lower limit value, good abrasion resistance can be obtained. By setting the density of the fibrous substrate to be not more than the upper limit value, good hand feeling can be obtained.

[0033] In the simulated shag leather sheet according to the present embodiment, the length of the above-mentioned raised hair is set to 200 to 500 μm. That is, the length of the raised hair in the state where the above-mentioned resin mixture is attached is 200 to 500 μm. By setting the length of the raised hair to be 200 μm or more, the generation of friction noise can be suppressed, and in addition, the abrasion resistance can be improved. In addition, by setting the length of the raised hair to be 500 μm or less, the abrasion resistance can be improved. The length of the raised hair is preferably 250 μm or more, more preferably 300 μm or more, and preferably 400 μm or less.

[0034] More specifically, when the fibrous substrate is a textile fabric, the length of the raised hair is preferably 200 to 400 μm. When the fibrous substrate is a knitted fabric, the length of the raised hair is preferably 250 to 500 μm, more preferably 250 to 400 μm, and further preferably 300 to 400 μm.

[0035] It should be noted that the length of the raised hairs mentioned above is the length of the raised hairs in the artificial raised-hair leather sheet to which the resin mixture is applied. However, the length of the raised hairs before applying the silicone resin and the polyurethane resin can be set within the same range as the above range.

[0036] The length of the raised hairs is measured as follows. That is, before measurement, the raised-hair surface is stroked 3 times along the direction opposite to the grain direction by hand to make the hairs stand up, and then, the length of the raised hairs (the length from the root of the hair to the tip of the hair) is measured. For the measurement, the vertical cross-section of the artificial raised-hair leather sheet is observed at 100 times magnification using a microscope (for example, manufactured by Keyence Corporation, VHX-200 / 100F), and the lengths of any 10 raised hairs are measured, and the average value thereof is calculated. Here, the direction opposite to the grain direction refers to the direction opposite to the grain direction, and the grain direction refers to the direction in which the raised hairs fall down.

[0037] The silicone resin and the polyurethane resin applied to the fibrous substrate are applied in the form of a mixture containing both as described above, and adhere to the surface of the fibers constituting the fibrous substrate.

[0038] The resin mixture containing the silicone resin and the polyurethane resin exists at least on the surface side where the raised hairs exist (that is, the raised-hair surface side) in the thickness direction of the fibrous substrate in order to impart abrasion resistance and suppress the generation of frictional noise. The above resin mixture can exist in the entire thickness direction of the fibrous substrate. At this time, the above resin mixture is applied to the fibrous substrate in such a manner that the raised hairs remain, rather than covering the entire raised-hair surface of the fibrous substrate in a film form (that is, not artificial grained leather). Accordingly, an artificial raised-hair leather sheet having the appearance and touch of suede or nubuck leather is obtained.

[0039] The silicone resin used in the present embodiment is not particularly limited, and examples thereof include: methylhydrogen silicone resin, amino-modified silicone resin, (meth)acrylic acid-modified silicone resin, and the like. These silicone resins can be used alone or in combination of two or more. Among them, from the viewpoints of suppressing the generation of frictional noise and abrasion resistance, methylhydrogen silicone resin is preferred. Here, the (meth)acrylic acid-modified silicone resin refers to: acrylic acid-modified silicone resin and / or methacrylic acid-modified silicone resin.

[0040] The silicone resin used in this embodiment is a resin having a main skeleton formed by siloxane bonds and is a resin having a three-dimensional network structure of a siloxane skeleton. In this regard, it is different from silicone oil and silicone rubber formed by linear polymers. This silicone resin is usually in a solid state, however, it can also be in a state with relatively low fluidity such as slurry-like or molasses-like at room temperature. It should be noted that the silicone resin can be a resin obtained by one-component curing through dehydration condensation of a silicone having a silanol group, and can also be a resin obtained by crosslinking and curing using a catalyst and a crosslinking agent. In addition, the silicone resin only needs to have a three-dimensional network structure of a siloxane skeleton at the stage of forming a plush leather-like sheet. For example, at the stage of the resin composition liquid before applying to the fibrous substrate or at the stage before heat treatment after applying the resin composition liquid to the fibrous substrate, it may not have a three-dimensional network structure.

[0041] The number average molecular weight of the silicone resin is not particularly limited, and preferably ranges from 1500 to 5000. By having a number average molecular weight of 1500 or more, it is easy to suppress the generation of frictional noise. By having a number average molecular weight of 5000 or less, a soft touch can be obtained. Here, the number average molecular weight of the silicone resin is a value obtained by measuring the silicone before crosslinking into a three-dimensional network structure. It should be noted that in this embodiment, for example, the number average molecular weight is calculated in the form of a polystyrene conversion value obtained by gel permeation chromatography (GPC).

[0042] The dynamic friction coefficient of the silicone resin is not particularly limited, and preferably ranges from 0.200 to 0.300, more preferably from 0.225 to 0.270. By having a dynamic friction coefficient of 0.200 or more, the touch can be improved. In addition, it has a smooth feeling and can give a touch close to that of natural leather. Furthermore, it can suppress hair loss caused by abrasion. By having a dynamic friction coefficient of 0.300 or less, the effect of suppressing the generation of frictional noise can be further improved. It should be noted that in this embodiment, the dynamic friction coefficient of the silicone resin can be obtained as follows: by measuring the dynamic friction coefficient of a silicone resin film made from an aqueous solution of the silicone resin prepared at the concentration of the formulation used when making the plush leather-like sheet (in the case where a catalyst and a crosslinking agent for crosslinking are required, it is a solution containing the catalyst and the crosslinking agent) using the method described later, the dynamic friction coefficient of the silicone resin can be obtained.

[0043] The amount of the silicone resin relative to the fibrous substrate is not particularly limited and may be appropriately set in a manner that achieves desired effects such as touch and suppression of frictional noise generation. Preferably, it is in the range of 0.10 to 2.0% by mass. When the amount of the silicone resin is 0.10% by mass or more, the effects such as touch improvement and frictional noise generation suppression can be enhanced. When the amount of the silicone resin is 2.0% by mass or less, frictional noise generation is easily suppressed. The amount of the silicone resin relative to the fibrous substrate may be 0.30% by mass or more, or may be 0.50% by mass or more. Additionally, it may be 1.8% by mass or less, or may be 1.0% by mass or less. Here, the amount of the silicone resin relative to the fibrous substrate means the adhesion amount (converted to solid content) of the silicone resin relative to the fibrous substrate after removing the amount of the above resin mixture, that is, the ratio of the silicone resin when the fibrous substrate is set to 100% by mass.

[0044] Examples of the polyurethane resin used in the present embodiment include polyether-based polyurethane resins, polyester-based polyurethane resins, polycarbonate-based polyurethane resins, and the like. These polyurethane resins may be used alone or in combination of two or more. Among them, from the viewpoint of abrasion resistance, a polycarbonate-based polyurethane resin is preferred.

[0045] Examples of the curing form of the polyurethane resin include one-component type, two-component curing type, moisture curing type, and the like. Among them, from the viewpoints of low environmental load and low work load, a water-based one-component type is preferred. Examples of the dispersion type of the water-based one-component type include self-emulsifying type and forced emulsifying type. From the viewpoints of high water resistance and high effect of preventing the silicone resin from peeling off the fibrous substrate, the forced emulsifying type is preferred.

[0046] The dynamic friction coefficient of the polyurethane resin is not particularly limited and is preferably in the range of 0.300 to 0.500. When the dynamic friction coefficient is 0.300 or more, the abrasion resistance is good, and in particular, fluffing due to abrasion is less likely to occur. When the dynamic friction coefficient is 0.500 or less, frictional noise generation is easily suppressed. It should be noted that in the present embodiment, the dynamic friction coefficient of the polyurethane resin can be obtained by measuring the dynamic friction coefficient of a polyurethane resin film made of an aqueous solution of the polyurethane resin prepared at the concentration of the formulation used when producing the artificial raised leather sheet by the method described later.

[0047] The amount of the polyurethane resin relative to the fibrous substrate is not particularly limited, and is preferably in the range of 1.0 to 7.0% by mass. When the amount of the polyurethane resin is 1% by mass or more, the silicone resin can be prevented from peeling off in the manufacturing process. In addition, the abrasion resistance can be improved. When the amount of the polyurethane resin is 7.0% by mass or less, the hand feeling can be prevented from becoming rough or the touch feeling can be prevented from being damaged. The amount of the polyurethane resin relative to the fibrous substrate can be 2.0% by mass or more, or can be 3.0% by mass or more. In addition, it can be 6.0% by mass or less, or can be 5.0% by mass or less. Here, the amount of the polyurethane resin relative to the fibrous substrate means the adhesion amount (in terms of solid content) of the polyurethane resin relative to the fibrous substrate after removing the amount of the above resin mixture, that is, the ratio of the polyurethane resin when the fibrous substrate is set to 100% by mass.

[0048] In addition, the mass ratio (in terms of solid content) of the amounts of the silicone resin and the polyurethane resin applied to the fibrous substrate is not particularly limited, and is preferably in the range of silicone resin: polyurethane resin = 1:2 to 1:52, and more preferably in the range of silicone resin: polyurethane resin = 1:2 to 1:40. When the amount of the polyurethane resin is 2 parts by mass or more relative to 1 part by mass of the silicone resin, the silicone resin can be prevented from peeling off in the manufacturing process. When the amount of the polyurethane resin is 52 parts by mass or less, more preferably 40 parts by mass or less, relative to 1 part by mass of the silicone resin, the silicone resin can fully exhibit the desired effects such as touch feeling and suppression of generation of friction noise. The amount of the polyurethane resin relative to 1 part by mass of the silicone resin is preferably 4 parts by mass or more, and can be 5 parts by mass or more. In addition, the amount of the polyurethane resin relative to 1 part by mass of the silicone resin is preferably 35 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and can be 8 parts by mass or less.

[0049] In the above resin mixture, in addition to the silicone resin and the polyurethane resin, various additives such as a catalyst, a matting agent, a smoothing agent, a surfactant, a filler, a leveling agent, a tackifier, a crosslinking agent, and a penetrant can be included within the range that does not impair the effects of the present embodiment.

[0050] The dynamic friction coefficient of the resin mixture is not particularly limited, and is preferably in the range of 0.180 to 0.350. When the dynamic friction coefficient is 0.180 or more, good wear resistance is achieved, and in addition, fluffing due to wear can be suppressed. When the dynamic friction coefficient is 0.350 or less, generation of frictional noise is easily suppressed. The dynamic friction coefficient of the resin mixture is more preferably 0.200 or more, further preferably 0.220 or more, and in addition, more preferably 0.300 or less, further preferably 0.250 or less. It should be noted that in the present embodiment, the dynamic friction coefficient of the resin mixture can be obtained by measuring the dynamic friction coefficient of a resin film produced from a resin composition solution prepared at a concentration according to the formulation when producing the flocked leather-like sheet, using the method described later, thereby obtaining the dynamic friction coefficient of the resin mixture.

[0051] The amount of the resin mixture adhered to the fibrous substrate is not particularly limited. In one embodiment, the total amount of the silicone resin and the polyurethane resin adhered to the fibrous substrate (i.e., the total amount of the silicone resin and the polyurethane resin), from the viewpoints of wear resistance and fluffing resistance, is preferably 10 g / m 2 or more, and in addition, from the viewpoint of the effect of suppressing frictional noise, is preferably 40 g / m 2 or less. The total amount in terms of solid content is more preferably 15 to 25 g / m 2 .

[0052] The static friction coefficient when the flocked surfaces of the flocked leather-like sheet according to the present embodiment are rubbed against each other is 0.660 to 1.300. If the static friction coefficient is too large or too small, frictional noise is generated. By setting it in the range of 0.660 to 1.300, generation of frictional noise can be suppressed. The static friction coefficient is more preferably 0.770 or more and 1.170 or less. The static friction coefficient of the flocked leather-like sheet can be adjusted using the length of the flocks, the amount of the resin mixture adhered, the types and mass ratios of the silicone resin and the polyurethane resin, etc. It should be noted that in the present embodiment, the static friction coefficient of the flocked leather-like sheet can be obtained by measurement using the method described later.

[0053] The manufacturing method of the flocked leather-like sheet according to the present embodiment is not particularly limited. The manufacturing method according to one embodiment successively includes: (1) a step of forming flocks composed of the fibers constituting the textile or knitted fabric on at least one surface of the fibrous substrate composed of the textile or knitted fabric, and (2) a step of applying a resin mixture containing a silicone resin and a polyurethane resin to the fibrous substrate formed with the flocks. In addition, it may include: (3) a step of subjecting the fibrous substrate to which the resin mixture has been applied to at least one kind of bath treatment selected from the group consisting of dyeing, scouring, and soaping.

[0054] In the process of forming the raised hairs in the above (1), the method of forming the raised hairs is not particularly limited, and known methods can be cited. For example, methods such as loosening the knitting structures of double-sided fabrics, sinker loop knitted fabrics, double-sided knitted fabrics, etc., methods using raising machines such as card clothing raising machines and emery raising machines, and hair implantation on fibrous substrates can be cited. Among them, from the viewpoints of appearance and touch, the method using a raising machine is preferred. The method using a raising machine includes full cut raising, half cut raising, and crimp raising, and the method of using half cut raising is more preferred. Here, full cut raising means raising in which all the fibers constituting the crimped raised yarn are cut. Half cut raising means raising in which a part of the fibers constituting the crimped raised yarn are cut. Crimp raising means raising in which the crimped raised yarn is not cut.

[0055] In the process of applying the resin mixture in the above (2), a resin combination liquid obtained by mixing a silicone resin and a polyurethane resin is applied to the fibrous substrate. The resin combination liquid is a composition for applying the above resin mixture to the fibrous substrate, contains a silicone resin and a polyurethane resin, and may also contain the above additives as optional components. It should be noted that the silicone resin in the resin combination liquid does not need to have a three-dimensional network structure as described above, and it can be finally crosslinked into a three-dimensional network structure by heat treatment or the like. In addition, the details of the silicone resin and the polyurethane resin are as described above.

[0056] In addition, the resin combination liquid may contain a solvent such as a highly polar solvent as needed. As the solvent, water is preferably used from the viewpoint of environmental load.

[0057] As a method of applying the resin combination liquid to the fibrous substrate, various conventionally known methods can be adopted and there is no particular limitation. For example, methods such as dipping, coating, spraying, printing, etc. can be cited. Among them, from the viewpoint of being able to uniformly apply the resin to the fibrous substrate, application by dipping is preferred.

[0058] When the method of applying the resin combination liquid to the fibrous substrate is dipping, the pick-up rate is not particularly limited, and it is preferably 20 to 80% by mass. By the pick-up rate being in this range, the desired amount can be applied evenly. The concentrations of the silicone resin and the polyurethane resin in the resin combination liquid are not particularly limited, and the total concentration of the two can be 13 to 17% by mass.

[0059] After applying the resin combination liquid to the fibrous substrate, heat treatment is carried out as needed. The purpose of carrying out the heat treatment is to evaporate the solvent in the resin combination liquid, thereby drying the resin. In addition, when using a catalyst or a crosslinking agent that undergoes a crosslinking reaction due to heat treatment, or when using a two-component curable resin, the purpose of carrying out the heat treatment is to promote the reaction and form a film with sufficient strength.

[0060] The heat treatment temperature can be 130 - 190°C, or can be 150 - 170°C. If the heat treatment temperature is 130°C or higher, the heat treatment will not take too much time, so the process load will not be too large. In addition, insufficient crosslinking of the resin can be prevented, so poor abrasion resistance can be prevented. If the heat treatment temperature is 190°C or lower, the feel of the sheet can be prevented from becoming rough and hard. In addition, the heat treatment time can be 1 - 3 minutes, or can be 2 - 3 minutes. If the heat treatment time is 1 minute or longer, insufficient crosslinking of the resin can be prevented, so poor abrasion resistance can be prevented. If the heat treatment time is within 3 minutes, the process load will not be too large either.

[0061] As the bath treatment process in the above (3), there is no particular limitation, and a desired process can be adopted. For example, a dyeing process, a scouring process, a soaping process, etc. can be cited. These processes are well-known processes in the past, and well-known methods in the past can be adopted.

[0062] If it is the artificial pile leather sheet involved in this embodiment, by applying a polyurethane resin and a silicone resin to a fibrous substrate composed of a textile or a knitted fabric, a desired feel can be obtained, and moreover, the generation of frictional noise on the surface of the sheet (i.e., the pile surface) can be suppressed. The frictional noise referred to here means: the frictional noise when the pile surfaces of the artificial pile leather sheets rub against each other, or when the pile surface rubs against other fiber products. Furthermore, shedding due to wear can be suppressed, and abrasion resistance can be improved. Therefore, if it is the artificial pile leather sheet involved in this embodiment, it is possible to solve the new problem of suppressing shedding and improving abrasion resistance while suppressing the generation of frictional noise for the artificial pile leather sheet having the appearance and feel of suede or nubuck leather.

[0063] In addition, if it is the manufacturing method of the artificial pile leather sheet involved in this embodiment, since the resin mixture is applied to the fibrous substrate before the bath treatment process, the abrasion resistance can be improved.

[0064] The use of the artificial pile leather sheet involved in this embodiment is not particularly limited. The artificial pile leather sheet can be used for various vehicle interior material uses represented by, for example, automotive interior materials such as car seats, headliner materials, instrument panels, door linings, or steering wheels. In addition, the artificial pile leather sheet can also be used for home decoration uses such as the epidermis of sofas and chairs, and fashion uses such as bags and shoes.

[0065] It should be noted that the upper and lower limits of each numerical range in this specification can be arbitrarily combined respectively.

[0066] Examples

[0067] Hereinafter, the present invention will be further described in detail using examples. However, the present invention is not limited to the following examples.

[0068] Each evaluation item is implemented according to the following method.

[0069] [Measurement of kinetic friction coefficient]

[0070] <Fabrication of resin film for measuring kinetic friction coefficient>

[0071] Using an applicator, a resin solution was coated on a release paper (KM130TPD, manufactured by Lintec Corporation) so that the film thickness of the obtained resin film was 500 μm, and then air-dried for 24 hours. Next, after drying at 80 °C for 3 hours using a dryer, further drying was performed at 130 °C for 30 minutes using a dryer to fabricate a resin film. Here, as the resin solution for film fabrication, in the measurement of the kinetic friction coefficient of silicone resin and polyurethane resin, a resin solution in which the silicone resin and polyurethane resin were respectively adjusted to the resin concentrations for measuring the kinetic friction coefficient shown in Table 1 was used. In addition, in the measurement of the kinetic friction coefficient of the resin mixture applied to the fibrous substrate, the resin combination solution of each formulation shown in Table 1 was used.

[0072] <Measurement method>

[0073] According to ASTM D1894, the kinetic friction coefficient was measured using Autograph AG-I (manufactured by Shimadzu Corporation). Specifically, a heavy object (width 62 mm, length 102 mm, weight 9.8 N) wound with a wool cloth (plain weave, warp: 19 tex, number of yarns 142 per 50 mm, weft: 15 tex, number of yarns 136 per 50 mm) without slack was placed on the test piece, and the kinetic friction coefficient when it was slid at a constant speed of 30 mm / minute was measured using a load cell installed in Autograph AG-I. It should be noted that as the test piece for kinetic friction measurement, the resin film in the above state with the release paper was used. The measurement was similarly performed for 3 test pieces, and the average value of the obtained numerical values was set as the kinetic friction coefficient.

[0074] [Measurement of static friction coefficient]

[0075] Two test pieces were taken as a group, and the coefficient of static friction was measured in accordance with ASTM D1894 using an Autograph AG-I (manufactured by Shimadzu Corporation). Specifically, a weight (width 62 mm, length 102 mm, weight 9.8 N) wound around one test piece without slack was placed on top of another test piece with the nap surfaces rubbing against each other along the grain direction, and the coefficient of static friction when it was made to slide at a constant speed of 30 mm / minute was measured using a load cell installed in the Autograph AG-I. The measurement was carried out in the same manner for three groups of test pieces, and the average value of the obtained numerical values was taken as the coefficient of static friction.

[0076] [Friction sound]

[0077] The test piece was placed on a horizontal table, and the magnitude of the friction sound when rubbing the surface (nap surface) of the test piece with the index finger was compared with a reference cloth, and a sensory evaluation was carried out according to the following evaluation criteria. Here, the reference cloth refers to the cloth before applying the resin composition liquid in each example and comparative example. It should be noted that an evaluation of B or above was judged as having no friction sound and was recorded as "none" in the table; an evaluation of C was judged as having a friction sound and was recorded as "yes" in the table.

[0078] <Evaluation criteria>

[0079] A: The magnitude of the friction sound is the same as that of the reference cloth.

[0080] B: The magnitude of the friction sound is slightly larger than that of the reference cloth.

[0081] C: The magnitude of the friction sound is significantly larger than that of the reference cloth.

[0082] [Abrasion resistance, lint shedding]

[0083] One test piece with a size of 70 mm in width and 300 mm in length was selected from the width direction of the strip material. Then, a polyurethane foam sheet with a size of 70 mm in width, 300 mm in length, and 10 mm in thickness was attached to the back and fixed to a flat abrasion tester T-TYPE (manufactured by Dairong Scientific Precision Instruments Co., Ltd.). A load of 9.8 N was applied to the friction member covered with cotton cloth (cotton canvas), and the surface (nap surface) of the test piece was rubbed. The friction member rubbed back and forth 10,000 times at a speed of 60 times back and forth per minute between 140 mm on the surface of the test piece. The test piece before and after friction was observed, and the abrasion resistance was evaluated according to the following criteria. In addition, a test piece with lint shedding was recorded as "yes" in the table, and a test piece without lint shedding was recorded as "none" in the table.

[0084] <Evaluation criteria>

[0085] Grade 5: The state of the worn part has not changed.

[0086] Level 4: The surface fibers are slightly wound along the worn surface, but are hardly noticeable.

[0087] Level 3: The surface fibers are wound along the worn surface, but are not noticeable.

[0088] Level 2: The surface fibers are wound along the worn surface and are very noticeable. Slight fuzzing occurs.

[0089] Level 1: The wound fibers and yarns are shed (fuzzing occurs), and the bottom line can be seen.

[0090] [Touch feeling]

[0091] For these two aspects of hardness (the higher the score, the softer; the lower the score, the harder) and texture (the higher the score, the more rough; the lower the score, the stickier), a score evaluation is carried out on a 5 - level scale (5 - 1). The respective scores are shown in the table, and based on the sum of the scores of the two evaluations, a comprehensive evaluation is carried out according to the following criteria.

[0092] <Evaluation criteria>

[0093] A: 9 - 10

[0094] B: 6 - 8

[0095] C: 4 - 5

[0096] D: 2 - 3

[0097] [Example 1]

[0098] A circular knitting loom of 24G is used. As the surface yarn and connecting yarn, a 70dtex / 216f polyester textured yarn is introduced, and as the back yarn, a 110dtex / 36f polyester textured yarn is introduced. A circular knitted fabric is knitted with a folded seam weave.

[0099] After the obtained circular knitted fabric is washed and dried, the following raising is carried out. That is, using a card raising machine equipped with a carding roller with 12 raising rollers and 12 reverse raising rollers, with a carding roller torque of 10 MPa and a fabric speed of 15 m / minute, the raising from the knitting start direction and the raising from the knitting end direction are alternately carried out 3 times to make the surface fluff of the circular knitted fabric stand up.

[0100] Next, after heat setting at 150 °C for 3 minutes using a heat setting machine, semi - cut raising is carried out through an emery raising machine with emery paper (#320). Specifically, with a surface rotation speed of the emery paper of 1000 rpm, a clearance of 0.8 mm, and a fabric speed of 8 m / minute, the surface (raising surface) of the circular knitted fabric is ground to obtain a circular knitted fabric with standing fluff. The gram weight of this circular knitted fabric is 400 g / m 2, with a thickness of 1000 μm, the single fiber fineness of the raised part is 0.3 dtex, the length of the standing hair is 320 μm, and the density of the fibrous substrate is 53 columns / 25.4 mm and 46 holes / 25.4 mm.

[0101] Using a calender, the obtained circular knitted fabric with standing hair was impregnated in the resin composition liquid of Formulation 1 shown in Table 1 at a lifting rate of 50% by mass. Next, using a heat setting machine, heat treatment was carried out at 170 °C for 3 minutes. Accordingly, a sheet obtained by impregnating and applying a silicone resin and a polyurethane resin to a circular knitted fabric with standing hair as a fibrous substrate was obtained. For the obtained sheet, using a jet dyeing machine, it was dyed with a disperse dye at 130 °C for 50 minutes, and then, using a heat setting machine, heat treatment was carried out at 130 °C for 3 minutes to obtain the imitation standing hair leather sheet of Example 1. The length of the standing hair of the obtained imitation standing hair leather sheet was 320 μm, and the static friction coefficient was 0.995.

[0102] The details and evaluation of the obtained imitation standing hair leather sheet are shown in Table 2. Regarding the "resin adhesion amount" in Table 2, the "total resin adhesion amount" is the total amount of the silicone resin and the polyurethane resin adhered to the fibrous substrate (converted by solid content). "Silicone resin (%)" is the amount of the silicone resin relative to the fibrous substrate. "Polyurethane resin (%)" is the amount of the polyurethane resin relative to the fibrous substrate. "Silicone resin: polyurethane resin" is the mass ratio of the silicone resin adhered to the fibrous substrate to the polyurethane resin. The same applies to Tables 3 and 4.

[0103] In the "imitation standing hair leather sheet" in Table 2, the "length of standing hair (μm)" and the "static friction coefficient" are the length of the standing hair and the static friction coefficient in the imitation standing hair leather sheet. The same applies to Tables 3 and 4.

[0104] [Examples 2 - 9]

[0105] As the resin composition liquid applied to the fibrous substrate, Formulations 2 - 9 shown in Table 1 were used as shown in Tables 2 and 3 respectively. Except for this, the imitation standing hair leather sheets of Examples 2 - 9 were obtained in the same manner as in Example 1. It should be noted that in Tables 2 and 3, regarding the density of the fibrous substrate, "53c / 46w" means: 53 columns / 25.4 mm and 46 holes / 25.4 mm.

[0106] [Example 10]

[0107] The same procedure as in Example 1 was followed except that the circular knit fabric was changed to a woven fabric (a satin woven fabric using a 2:1 ratio of 117 dtex / 36f polyester textured yarn (17-split split yarn) and 56 dtex / 24f polyester textured yarn, and a weft of 167 dtex / 48f polyester textured yarn). The imitation raised suede leather sheet of Example 10 was obtained. The woven fabric had a grammage of 250 g / m2 after raising. 2 The raised fabric was 1000 μm thick, with a single fiber fineness of 0.19 dtex and a nap length of 300 μm. The warp density of the fibrous substrate was 360 yarns / 25.4 mm and the weft density was 63 yarns / 25.4 mm. The raised fabric was subjected to the same impregnation treatment and dyeing as in Example 1.

[0108] [Examples 11 to 14]

[0109] Except for adjusting the number of napping times and changing the nap length as shown in Table 3, similar procedures to Example 1 were carried out to obtain imitation napped leather sheets of Examples 11 to 14.

[0110] [Comparative Example 1]

[0111] A simulated napped leather sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that Prescription 11 shown in Table 1 was used as the resin composition liquid applied to the fibrous base material.

[0112] [Comparative Example 2]

[0113] A simulated napped leather sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that Prescription 10 shown in Table 1 was used as the resin composition liquid applied to the fibrous base material.

[0114] [Comparative Example 3]

[0115] A nonwoven fabric (manufactured by Asahi Kasei Corporation, 3021B, weight 230 g / m2) in which a polycarbonate-based polyurethane resin was attached to the fibers at a concentration of 8.9% by mass was used. 2 ) instead of circular knitted fabric. The nonwoven fabric was subjected to the same raising treatment as in Example 1 to obtain a raised nonwoven fabric. The total weight of the fiber base material and the polyurethane resin in the obtained raised nonwoven fabric was 230 g / m 2 The weight of the fiber substrate is 211g / m 2 The thickness was 900 μm, the single fiber fineness of the raised portion was 0.15 dtex, and the length of the raised naps was 130 μm. The resin composition liquid for treating the raised nonwoven fabric was formulated as Recipe 10 shown in Table 1. The resin composition liquid was applied, dyed, and heat-treated in the same manner as in Example 1 to obtain a simulated raised nap leather sheet of Comparative Example 3.

[0116] [Comparative Examples 4 and 5]

[0117] The number of raising operations was adjusted, and the length of the raised hair was changed as shown in Table 4. Other than that, the faux raised-hair leather sheets of Comparative Examples 4 and 5 were obtained in the same manner as in Example 1.

[0118] The details of each component in Table 1 are as follows.

[0119] <Silicone resin>

[0120] · Silicone resin solution 1: A mixture of 50 parts by mass of KF99 (manufactured by Shin-Etsu Chemical Co., Ltd., methylhydrogenpolysiloxane, solid content 100% by mass, forming a three-dimensional network structure by using in combination with a catalyst and performing heat treatment), 2 parts by mass of polyoxyethylene polyoxypropylene glycol (manufactured by Fujifilm Wako Pure Chemical Corporation, dispersant, solid content 100% by mass), and 48 parts by mass of water.

[0121] · Nicca Silicon AMZ-3: Amino-modified silicone resin (solid content 36% by mass) manufactured by Nikkawa Chemical Co., Ltd.

[0122] <Silicone oil>

[0123] · Eras finish S-65: Dimethyl silicone oil (active ingredient 42% by mass) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0124] <Polyurethane resin>

[0125] · Hydran WLI-620AR: Polycarbonate-based polyurethane resin (aqueous one-component type, forced emulsification type, solid content 50% by mass) manufactured by DIC Corporation.

[0126] · Evaphanol APC-66: Polycarbonate-based polyurethane resin (aqueous one-component type, forced emulsification type, solid content 36% by mass) manufactured by Nikkawa Chemical Co., Ltd.

[0127] <Catalyst for crosslinking of silicone resin>

[0128] · Catalyst solution 1: A mixture of 14 parts by mass of zinc stearate (manufactured by Fujifilm Wako Pure Chemical Corporation, catalyst, solid content 100% by mass), 4 parts by mass of polyoxyethylene polyoxypropylene glycol (manufactured by Fujifilm Wako Pure Chemical Corporation, dispersant, solid content 100% by mass), and 82 parts by mass of water

[0129] [Table 1]

[0130]

[0131] [Table 2]

[0132]

[0133] (In Table 2, MHS: Methylhydrogen polysiloxane resin

[0134] PC series: Polycarbonate-based polyurethane resin)

[0135] [Table 3]

[0136]

[0137] (In Table 3, MHS: Methylhydrogen polysiloxane resin

[0138] PC series: Polycarbonate-based polyurethane resin)

[0139] [Table 4]

[0140]

[0141] (In Table 4, MHS: Methylhydrogen polysiloxane resin

[0142] DMS: Dimethyl silicone oil

[0143] PC series: Polycarbonate-based polyurethane resin)

[0144] The results are shown in Tables 2 to 4. The artificial pile leather sheet of Comparative Example 1 to which the polyurethane resin and the silicone oil were applied had a significantly louder friction sound than the reference cloth. In addition, the artificial pile leather sheet of Comparative Example 2 to which only the silicone resin was applied had not only a louder friction sound than the reference cloth, but also poorer abrasion resistance, fluffing, and touch. In addition, the artificial pile leather sheet of Comparative Example 3 using non-woven fabric as the fibrous substrate was poor in abrasion resistance and fluffing. Further, the artificial pile leather sheet of Comparative Example 4 having a pile length of less than 200 μm had a louder friction sound than the reference cloth, and in addition, it was found that the base tissue was likely to be exposed due to wear, resulting in a tendency of reduced abrasion resistance. The artificial pile leather sheet of Comparative Example 5 having a pile length exceeding 500 μm was poor in abrasion resistance.

[0145] On the other hand, in the case of the artificial pile leather sheets of Examples 1 to 14, there was no fluffing, and in addition, they had excellent abrasion resistance, the friction sound was significantly improved, and the effect of suppressing the friction sound was excellent. In particular, in the case of Examples 1, 2, 4 to 6, 8 to 14, the touch was also excellent. From Examples 1, 11 to 14 and Comparative Example 5, the following tendency was obtained, that is, as the pile becomes longer, the stickiness becomes larger in terms of touch.

[0146] Symbol Explanation

[0147] 10... Artificial pile leather sheet, 12... Fibrous substrate, 14... Pile, 16... Pile surface.

Claims

1. An artificial pilose leather sheet, comprising: A fibrous substrate composed of a woven fabric or a knitted fabric; And A mixture applied to the fibrous substrate and containing a silicone resin and a polyurethane resin, The artificial pilose leather sheet is characterized in that On the surface of the sheet, there is a pilose surface with erected hairs, the erected hairs are composed of the fibers constituting the woven fabric or the knitted fabric and are attached with the mixture, and the mixture exists at least on the surface side where the erected hairs are present in the thickness direction of the fibrous substrate, The silicone resin has a siloxane skeleton with a three-dimensional network structure, The length of the erected hairs in the state of being attached with the mixture is 200 - 500 μm, The static friction coefficient when the pilose surfaces are rubbed against each other is 0.660 - 1.300, The mass ratio of the silicone resin to the polyurethane resin is 1:2 - 1:52, The total amount of the silicone resin and the polyurethane resin is 10 to 40 g / m 2 .

2. The artificial pilose leather sheet according to claim 1, characterized in that The silicone resin contains at least one selected from the group consisting of methylhydrogen silicone resin, amino-modified silicone resin, and (meth)acrylic acid-modified silicone resin.

3. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The amount of the silicone resin relative to the fibrous substrate is 0.10 - 2.0% by mass.

4. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The dynamic friction coefficient of the mixture is 0.180 - 0.

350.

5. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The dynamic friction coefficient of the silicone resin is 0.200 - 0.300, and the dynamic friction coefficient of the polyurethane resin is 0.300 - 0.

500.

6. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The number average molecular weight of the silicone resin before crosslinking is 1500 - 5000.

7. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The amount of the polyurethane resin relative to the fibrous substrate is 1.0 - 7.0% by mass.

8. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The fineness of the fibers constituting the erected hairs is 0.1 - 0.4 dtex.

9. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The fineness of the yarns constituting the fibrous substrate is 50 - 200 dtex.

10. The artificial pilose leather sheet according to claim 1 or 2, characterized in that The thickness of the fibrous substrate is 600 - 1500 μm.

11. A method for manufacturing a sheet-like object imitating pilomotor leather, characterized in that, Comprising: Forming erected hairs composed of the fibers constituting the woven fabric or the knitted fabric on at least one side of the fibrous substrate composed of the woven fabric or the knitted fabric, and Applying a mixture containing a silicone resin and a polyurethane resin to the fibrous substrate formed with the erected hairs, thereby obtaining an artificial pilose leather sheet, The surface of the imitation pilose leather sheet has a pilose surface, and the pilose surface has pilose hairs to which the mixture is attached. The mixture is present at least on the surface side where the pilose hairs are present in the thickness direction of the fibrous substrate. The silicone resin has a siloxane skeleton with a three-dimensional network structure. The length of the pilose hairs in the state where the mixture is attached is 200 to 500 μm. The static friction coefficient when the pilose surfaces are rubbed against each other is 0.660 to 1.

300. The mass ratio of the silicone resin to the polyurethane resin is 1:2 to 1:52, and the total amount of the silicone resin and the polyurethane resin is 10 to 40 g / m 2 .

12. The manufacturing method of the imitation pilose leather sheet according to claim 11, characterized in that, Further comprising: The fibrous substrate to which the mixture has been applied is subjected to in-bath treatment, and the in-bath treatment is at least one selected from the group consisting of dyeing, scouring, and soaping.

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